JP2007277201A - Aromatic dihydroxy compound and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic dihydroxy compound and an industrially advantageous method for producing the same. <P>SOLUTION: A compound represented by general formula (1) (wherein R on a benzene ring is a hydrogen atom or an alkyl group; R' is an alkyl group; m, n, and o are each an integer of 1-4; and l is an integer of 1-3) is reacted in an aprotic polar solvent in the presence of a tertiary-amine mineral acid salt to produce an aromatic dihydroxy compound represented by general formula (2). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aromatic dihydroxy compound useful as a monomer for various resins and a method for producing the same.

The aromatic dihydroxy compound is a compound useful as a monomer for aromatic polycarbonate, aromatic polyurethane, aromatic polyester, epoxy resin and the like.
Patent Document 1 describes a heat-sensitive recording paper using 1,3-bis (3-hydroxyphenoxy) benzene as a developer, but does not describe the production method, physical properties, and the like.

  As a method for producing an aromatic dihydroxy compound, a method in which a corresponding aromatic dialkoxy compound and hydrobromic acid are reacted to convert an alkyl group into a hydroxyl group is known, but the yield is only about 40%. (Patent Document 2).

Further, a method of using hydroiodide as a pyridine hydrohalide and reacting in N, N-dimethylformamide (DMF) or N, N-dimethylacetamide (DMAC) is known. The rate is only 28% (Patent Document 3). Furthermore, even if hydroiodic acid supported on a special resin (Reillex-pyridine-TM-402 resin) is allowed to act, the yield cannot be said to be sufficient (Patent Document 3).
Japanese Patent Laid-Open No. 1-222990 Japanese Patent Laid-Open No. 3-63179 Special table 2003-525290 gazette

  An object of the present invention is to provide an aromatic dihydroxy compound exhibiting characteristic physical properties as compared with conventional dihydroxy compounds when used as a resin raw material, and industrially advantageous to obtain the aromatic dihydroxy compounds in a high yield. It is to provide a manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have responded to an aromatic dihydroxy compound characterized in that all of the benzene rings are linked at the m-position via an oxygen atom. By reacting the aromatic dialkoxy compound in the presence of a tertiary amine mineral salt in an aprotic polar solvent (excluding N, N-dimethylformamide and N, N-dimethylacetamide). It was found to be obtained in a yield. This aromatic dialkoxy compound can be obtained by reacting the corresponding aromatic dihalogeno compound in an aprotic polar solvent in the presence of an alcohol metal salt.

That is, the present invention relates to the following.
[1] General formula (1):

(Wherein R on the same and different benzene rings each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, m, n, o) Are each independently an integer of 1 to 4, and l is an integer of 1 to 3)
In the presence of a tertiary amine mineral salt in an aprotic polar solvent (excluding N, N-dimethylformamide and N, N-dimethylacetamide). :

(In the formula, R on the same and different benzene rings each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m, n and o each independently represents an integer of 1 to 4; Represents an integer of 1 to 3)
The manufacturing method of the aromatic dihydroxy compound represented by these.
[2] An aromatic dihydroxy compound represented by the general formula (2).

  According to the present invention, it is possible to provide a novel aromatic dihydroxy compound in which all of the benzene rings are linked at the m-position via an oxygen atom, and an industrially advantageous production method of the compound.

  General formula (2):

(In the formula, R on the same and different benzene rings each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m, n and o each independently represents an integer of 1 to 4; Represents an integer of 1 to 3)
Is characterized in that all of the benzene rings are linked at the m-position via an oxygen atom.

  R in General formula (2) represents a hydrogen atom or a C1-C4 alkyl group each independently, and l shows the integer of 1-3.

Examples of the compound represented by the general formula (2) include 1,3-bis (3-hydroxyphenoxy) benzene, 1,3-bis (3-hydroxy-5-methylphenoxy) benzene, and 1,3-bis. (3-hydroxy-2-methylphenoxy) benzene, 1,3-bis (3-hydroxy-5-methylphenoxy) -4-methylbenzene, 3,3′-bis (3-hydroxyphenoxy) diphenyl ether, 3,3 '-Bis (3-hydroxy-5-methylphenoxy) diphenyl ether, 1,3-bis (3- (3-hydroxyphenoxy) phenoxy) benzene, 1,3-bis (3- (3-hydroxy-2-methylphenoxy) ) Phenoxy) benzene, 1,3-bis (3- (3-hydroxyphenoxy) phenoxy) -4-ethylbenzene, 1,3-bis ( 3- (3-Hydroxy-5-methylphenoxy) phenoxy) -2,5-dimethylbenzene and the like can be mentioned, but are not limited to these compounds.
The compound represented by the general formula (2) is represented by the general formula (1):

(Wherein R on the same and different benzene rings each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, m, n, o) Are each independently an integer of 1 to 4, and l is an integer of 1 to 3)
Is reacted in an aprotic polar solvent (excluding N, N-dimethylformamide and N, N-dimethylacetamide) in the presence of a mineral salt of a tertiary amine. be able to.

  R in the general formula (1) each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, and l represents an integer of 1 to 3. Show.

  Examples of the compound represented by the general formula (1) include 1,3-bis (3-methoxyphenoxy) benzene, 1,3-bis (3-methoxy-5-methylphenoxy) benzene, and 1,3-bis. (3-methoxy-2-methylphenoxy) benzene, 1,3-bis (3-methoxy-5-methylphenoxy) -4-methylbenzene, 3,3′-bis (3-methoxyphenoxy) diphenyl ether, 3,3 '-Bis (3-methoxy-5-methylphenoxy) diphenyl ether, 1,3-bis (3- (3-methoxyphenoxy) phenoxy) benzene, 1,3-bis (3- (3-methoxy-2-methylphenoxy) ) Phenoxy) benzene, 1,3-bis (3- (3-methoxyphenoxy) phenoxy) -4-ethylbenzene, 1,3-bis (3- (3-me Xyl-5-methylphenoxy) phenoxy) -2,5-dimethylbenzene, 1,3-bis (3-ethoxyphenoxy) benzene, 1,3-bis (3-ethoxy-5-methylphenoxy) benzene, 1,3 -Bis (3-ethoxy-2-methylphenoxy) benzene, 1,3-bis (3-ethoxy-5-methylphenoxy) -4-methylbenzene, 3,3'-bis (3-ethoxyphenoxy) diphenyl ether, 3 , 3'-bis (3-ethoxy-5-methylphenoxy) diphenyl ether, 1,3-bis (3- (3-ethoxyphenoxy) phenoxy) benzene, 1,3-bis (3- (3-ethoxy-2- Methylphenoxy) phenoxy) benzene, 1,3-bis (3- (3-ethoxyphenoxy) phenoxy) -4-ethylbenzene, 1 3- bis (3- (3-ethoxy-5-methyl) phenoxy) -2,5-but-dimethylbenzene, and the like, are not limited only to these compounds.

  The tertiary amine mineral acid salt used in the production method of the present invention is a mineral acid adduct of a tertiary amine. Specific examples include triethylamine hydrochloride, triethylamine hydrobromide, dimethylaniline hydrochloride, pyridine hydrochloride, pyridine hydrobromide, pyridine hydrofluoride, etc. Among them, pyridine hydrochloride, pyridine Hydrobromide is preferred, but is not limited to these. Further, these tertiary amine mineral acid salts may be prepared in the reaction system by separately adding the corresponding tertiary amine and mineral acid. The amount of the tertiary amine mineral acid salt used is preferably 2 to 50 moles, more preferably 4 to 20 moles, relative to the compound of the general formula (1) from the viewpoint of yield and economy. Moreover, when preparing and adding a tertiary amine and a mineral acid separately in a reaction system, if a tertiary amine mineral acid salt is the said range, either may be added excessively.

  This reaction is carried out using an aprotic polar solvent (excluding N, N-dimethylformamide and N, N-dimethylacetamide). A solvent that does not impair the reactivity, dissolves the tertiary amine mineral acid salt, and does not react with these salts is desirable. Among them, general formula (3):

Wherein R ″ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ′ ″ is an alkyl group having 1 to 4 carbon atoms, X is a carbon atom or nitrogen atom, Y is an oxygen atom or Represents a nitrogen atom, and n represents an integer of 2 to 5. However, when X is a nitrogen atom, R ″ is an alkyl group having 1 to 4 carbon atoms, and when Y is an oxygen atom, the substituent R ′ Does not have '')
The compound represented by these is preferable. Of the compounds represented by the general formula (3), a cyclic amide, a cyclic imide, or a cyclic lactone compound is more preferable.
Specific examples include N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), γ-butyrolactone, etc. Among them, DMI is most preferable. The amount of the aprotic polar solvent used is 1 to 50 times by weight, preferably 1 to 20 times by weight with respect to the general formula (1). If it is 1 weight times or more, it is preferable in that it is possible to avoid difficulty in stirring due to salt precipitation, and if it is 20 weight times or less, it is preferable from the viewpoint of economy.

  The reaction temperature is usually preferably 50 to 250 ° C. from the viewpoint of reaction time and yield. Moreover, when raising temperature beyond the boiling point of a solvent, it is also possible to carry out under pressure using an autoclave.

As a method for taking out after completion of the reaction, for example, the reaction mixture is directly discharged into water, or the reaction mixture is concentrated under reduced pressure, and then discharged into water. After neutralization and extraction with an organic solvent, The target product can be obtained by concentrating the organic layer. The organic solvent is not particularly limited as long as it dissolves the target product and is not miscible with water, but is preferably toluene, xylene, monochlorobenzene, diethyl ether, ethyl acetate, butyl acetate, methyl isobutyl ketone, etc. Methyl isobutyl ketone is particularly preferred.
Further, it can be purified by a method such as silica gel column chromatography or extraction.

  The compound represented by general formula (1) is, for example, general formula (4):

(Wherein R on the same and different benzene rings each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and m, n and o each independently represents 1 to An integer of 4 and l represents an integer of 1 to 3)
A dihalogeno compound represented by general formula (5):

(In the formula, R ′ represents an alkyl group having 1 to 4 carbon atoms, and M represents an alkali metal)
It is obtained by reacting an alcohol metal salt represented by the formula (1) in an aprotic polar solvent.

  Examples of the dihalogeno compound represented by the general formula (4) include 1,3-bis (3-chlorophenoxy) benzene, 1,3-bis (3-chloro-5-methylphenoxy) benzene, 1,3- Bis (3-chloro-2-methylphenoxy) benzene, 1,3-bis (3-chloro-5-methylphenoxy) -4-methylbenzene, 3,3′-bis (3-chlorophenoxy) diphenyl ether, 3, 3′-bis (3-chloro-5-methylphenoxy) diphenyl ether, 1,3-bis (3- (3-chlorophenoxy) phenoxy) benzene, 1,3-bis (3- (3-chloro-2-methyl) Phenoxy) phenoxy) benzene, 1,3-bis (3- (3-chlorophenoxy) phenoxy) -4-ethylbenzene, 1,3-bis (3- (3-chloro-5) Methyl) phenoxy) -2,5-dimethylbenzene dichloro compounds such as,

1,3-bis (3-bromophenoxy) benzene, 1,3-bis (3-bromo-5-methylphenoxy) benzene, 1,3-bis (3-bromo-2-methylphenoxy) benzene, 1,3 -Bis (3-bromo-5-methylphenoxy) -4-methylbenzene, 3,3'-bis (3-bromophenoxy) diphenyl ether, 3,3'-bis (3-bromo-5-methylphenoxy) diphenyl ether, 1,3-bis (3- (3-bromophenoxy) phenoxy) benzene, 1,3-bis (3- (3-bromo-2-methylphenoxy) phenoxy) benzene, 1,3-bis (3- (3 -Bromophenoxy) phenoxy) -4-ethylbenzene, 1,3-bis (3- (3-bromo-5-methylphenoxy) phenoxy) -2,5-dimethylbenze Dibromo compounds such as,

1,3-bis (3-fluorophenoxy) benzene, 1,3-bis (3-fluoro-5-methylphenoxy) benzene, 1,3-bis (3-fluoro-2-methylphenoxy) benzene, 1,3 -Bis (3-fluoro-5-methylphenoxy) -4-methylbenzene, 3,3'-bis (3-fluorophenoxy) diphenyl ether, 3,3'-bis (3-fluoro-5-methylphenoxy) diphenyl ether, 1,3-bis (3- (3-fluorophenoxy) phenoxy) benzene, 1,3-bis (3- (3-fluoro-2-methylphenoxy) phenoxy) benzene, 1,3-bis (3- (3 -Fluorophenoxy) phenoxy) -4-ethylbenzene, 1,3-bis (3- (3-fluoro-5-methylphenoxy) phenoxy) -2 It includes difluoro compounds such as 5-dimethylbenzene. Among these, a difluoro compound is a preferable compound for applying the production method of the present invention.

  As the alcohol metal salt represented by the general formula (5), a corresponding alkali metal salt of alcohol is used, and examples of the alkali metal include sodium and potassium. Specific examples include sodium methylate, sodium ethylate, potassium t-butyrate and the like. The amount used is preferably 2 to 50 moles, more preferably 2 to 20 moles, relative to the general formula (4) from the viewpoint of yield and economy. These alcohol metal salts may be added as solids as they are, but may be added as a solution using a corresponding alcohol solvent. If the reaction temperature cannot be maintained by adding alcohol, the alcohol can be distilled off.

The solvent used in the reaction of the dihalogeno compound represented by the general formula (4) and the alcohol metal salt represented by the general formula (5) is preferably an aprotic polar solvent. The aprotic polar solvent in this case is not particularly limited, and examples thereof include DMF, DMAC, NMP, DMI, γ-butyrolactone, dimethyl sulfoxide, and sulfolane. Among these, DMI is particularly preferable. The amount of the aprotic polar solvent used is 1 to 50 times by weight, preferably 1 to 20 times by weight with respect to the general formula (4). It is preferable that the amount is 1 times by weight or more from the viewpoint of avoiding difficulty in stirring due to precipitation of by-produced inorganic salts, and is preferably 20 times by weight or less from the viewpoint of economy.
This reaction is preferably 50 to 250 ° C. from the viewpoint of reaction time and yield.
As a method for taking out the reaction after completion of the reaction, for example, the reaction mixture is directly filtered to remove the precipitated inorganic salt and then extracted with an organic solvent, or the reaction mixture is left as it is or neutralized, and the solvent is removed under reduced pressure. And the organic solvent added for extraction is filtered to remove the precipitated inorganic salt. The organic layer is neutralized and washed with water, and then the solution is concentrated to obtain the desired product. Furthermore, it is also possible to purify using general methods such as silica gel column chromatography and distillation.

  The compound of General formula (4) can be manufactured with reference to the method described in Unexamined-Japanese-Patent No. 2004-2265.

  The compound represented by the general formula (2) can be used for the production of aromatic polycarbonate, aromatic polyurethane, aromatic polyester, epoxy resin and the like. For example, a flexible polycarbonate polymer can be produced by reacting the compound represented by the general formula (2) with phosgene.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
The analysis relied on high performance liquid chromatography (hereinafter abbreviated as “HPLC”) analysis. The analysis conditions are as follows.
[Analysis of 1,3-bis (3-methoxyphenoxy) benzene]
Column: YMC-Pack ODS-A A-312 6.0φmm × 150mm (manufactured by YMC)
・ Column temperature: 40 ℃
・ Detection wavelength: 254nm
Eluent: acetonitrile / water / 85% phosphoric acid = 700/300/1 (vol / vol / vol)
[Analysis of 1,3-bis (3-hydroxyphenoxy) benzene]
Column: YMC-Pack ODS-A A-312 6.0φmm × 150mm (manufactured by YMC)
・ Column temperature: 40 ℃
・ Detection wavelength: 254nm
Eluent: acetonitrile / water / 85% phosphoric acid = 500/500/1 (vol / vol / vol)

Production Example 1 Production of 1,3-bis (3-methoxyphenoxy) benzene In a 500 ml four-necked flask equipped with a reflux apparatus equipped with a stirrer and Dean Stark and an air blowing tube, 1,3-bis was added. 149.1 g of (3-fluorophenoxy) benzene and 298.2 g of DMI were charged, and the temperature was raised to 120 ° C. in a nitrogen atmosphere. Using a dropping funnel, 222.1 g of a 28% by mass sodium methylate methanol solution was added dropwise over about 3.5 hours. During the dropping, the distilled methanol was withdrawn, and the temperature of the reaction mixture was kept constant at 120 ° C. After further reacting for 3 hours, the mixture was cooled to room temperature. The reaction mixture was filtered, the filtrate was extracted with toluene, neutralized and washed with water, and then the organic layer was concentrated to obtain 148.9 g of colorless oily 1,3-bis (3-methoxyphenoxy) benzene. The purity by HPLC was 92.3% and contained 3.3% of 1- (3-hydroxyphenoxy) -3- (3-methoxyphenoxy) benzene. When the obtained 1,3-bis (3-methoxyphenoxy) benzene was purified by distillation under reduced pressure, a purified product having an HPLC purity of 99.3% was obtained.

Analytical data of 1,3-bis (3-methoxyphenoxy) benzene is as follows.
MS (EI (Pos.) Method) M / Z = 322 (M +)
1H-NMR (CDCL3): δ
3.8 (s, 6H), 6.5-6.8 (m, 9H), 7.1-7.3 (m, 3H)
13C-NMR (CDCL3): δ
55.3, 105.1, 109.2, 109.7, 111.2, 113.5, 130 (d), 157.9, 158.3, 160.9
IR spectrum: as shown in FIG.

Production of 1,3-bis (3-hydroxyphenoxy) benzene (DMI solvent)
9500 g of pyridine hydrochloride and 200 g of DMI were charged into a 500 ml four-necked flask equipped with a stirrer, a reflux device and an air blowing tube, and the temperature was raised in a nitrogen atmosphere. When the internal temperature reached 74 ° C., the pyridine hydrochloride crystals were completely dissolved. Further, after the temperature was raised to 180 ° C., 66.6 g of 1,3-bis (3-methoxyphenoxy) benzene was added dropwise over 5 hours using a dropping funnel. The reaction was terminated after stirring for 14 hours at 180 ° C. Thereafter, the reaction mixture was cooled to room temperature, but no precipitation of crystals was observed. The reaction mixture was charged with 100 g of water and extracted with 266 g of methyl isobutyl ketone (MIBK). After extraction, the organic layer was washed with dilute hydrochloric acid and further washed with water to obtain a MIBK solution of 1,3-bis (3-hydroxyphenoxy) benzene. The purity of HPLC excluding the solvent was 97.5%. To this solution, 250 g of water was added, and 4 g of a 20% by mass aqueous caustic soda solution was charged, followed by separation after stirring. The organic layer was further charged with 250 g of water, charged with 77.5 g of 20% by weight caustic soda, and separated after stirring. The aqueous layer was charged with 266 g of MIBK, and the aqueous layer was neutralized with 17.5% by mass hydrochloric acid. After liquid separation, the organic layer was washed with water, and 1 g of activated carbon was added to the organic layer and stirred for 30 minutes, followed by filtration. The filtrate was concentrated, and 57.1 g of 1,3-bis (3-hydroxyphenoxy) benzene was added. Obtained. The purity by HPLC analysis was 99.1%. The isolated yield of 1,3-bis (3-hydroxyphenoxy) benzene was 93.9%.

Analysis data of 1,3-bis (3-hydroxyphenoxy) benzene is as follows.
MS (EI (Pos.) Method) M / Z = 294 (M +)
1H-NMR (CDCL3): δ
5.5-5.7 (br, 2H), 6.4-6.5 (t, 2H), 6.5-6.6 (m, 4H), 6.6-6.7 (t, 1H), 6.7-6.8 (dd, 2H), 7.1-7.2 (t , 2H), 7.2-7.3 (m, 1H)
13C-NMR (CDCL3): δ
106.0, 110.2, 110.5, 111.3, 114.1, 130.5, 156.6, 157.9, 158.1
IR spectrum: as shown in FIG.

(Comparative Example 1) Production of 1,3-bis (3-hydroxyphenoxy) benzene (no solvent)
A 100 ml four-necked flask equipped with a stirrer, a reflux device and an air blowing tube was charged with 10.8 g of pyridine hydrochloride and 5.0 g of 1,3-bis (3-methoxyphenoxy) benzene, and a nitrogen atmosphere. The temperature rose below. In the reaction mixture, pyridine hydrochloride remained solid and stirring was very difficult. When the temperature exceeded 150 ° C., a uniform solution was obtained, but during the reaction at the same temperature after raising the temperature to 180 ° C., a sublimate considered to be pyridine hydrochloride was deposited on the upper portion of the flask. Since the refluxing device was blocked during the reaction, the reaction was continued while scraping off the sublimate with a spatula. Since it was confirmed that the reaction was completed in 8 hours, when the reaction mixture was cooled to room temperature, crystals were precipitated from around 140 ° C. and stirring was difficult. The reaction mixture was charged with 10 g of water and extracted with 20 g of MIBK. Acid washing and water washing were performed, and the organic layer was concentrated to obtain 1,3- (3-hydroxyphenoxy) benzene. The purity by HPLC analysis was 98.2%.

(Comparative Example 2) Production of 1,3-bis (3-hydroxyphenoxy) benzene (DMF solvent)
A 200 ml autoclave (material: Hasteroid C) attached with a stirrer and pressure gauge was charged with 21.5 g of pyridine hydrochloride, 10.0 g of 1,3-bis (3-methoxyphenoxy) benzene and 50 g of DMF. Then, heating was started after sealing in a nitrogen atmosphere. An increase in internal pressure was observed from 150 ° C., and since the pressure suddenly increased from around 160 ° C. and exceeded 1 MPa, the reaction was stopped. Even after cooling, the residual pressure was 1 MPa. When the reaction mixture was analyzed, 1,3-bis (3-hydroxyphenoxy) benzene was not produced.

(Reference Example) Production of polycarbonate polymer by phosgenation of 1,3-bis (3-hydroxyphenoxy) benzene In a 1 L flask equipped with a stirrer, 55.9 g of 1,3-bis (3-hydroxyphenoxy) benzene (0.19 mol), 75.9 g (0.95 mol) of pyridine, and 200 g of dichloromethane were cooled to 0 ° C. under nitrogen flow, and 26.6 g (0.27 mol) of phosgene was blown into 350 g of dichloromethane. The solution was added dropwise over 5 hours. After the dropwise addition, the mixture was further kept at 0 ° C. for 2 hours, and then 1.0 g (0.0092 mol) of benzyl alcohol was added, and the mixture was further kept for 1 hour, and then charged with 24 g of water. Was dripped. The lower organic layer was extracted and washed with water repeatedly.

Next, 1500 mL of methanol was charged into a 3 L flask equipped with a stirrer and Dean Stark and heated to 40 ° C., and then the above organic layer was dropped over 2 hours and crystallized under nitrogen flow. The crystals were filtered, washed with methanol, and then dried to obtain 31 g of white crystals. A part of the crystals was dissolved in chloroform and the molecular weight was confirmed by gel permeation chromatography (GPC). The weight average molecular weight was MW: 39000 (polystyrene conversion).
0.5 g of a sample was weighed, a UPILEX film (Ube Industries, Ltd. polyimide film) was put inside, sandwiched between spacers, and heated and melted with a hot press for 8 minutes. After melting, the film was adjusted by cooling with a press at about 50 kg / cm. The obtained film was colorless and transparent, easily bendable, stretchable, and rich in restoring force.
[Measurement of molecular weight of polycarbonate polymer]
・ Column: Shodex KF-802 8.0φmm × 300mm (made by Showa Denko KK)
・ Column temperature: 40 ℃
・ Detector: RI
・ Eluent: Chloroform

  The aromatic dihydroxy compound of the present invention is useful as a monomer for aromatic polycarbonate, aromatic polyurethane, aromatic polyester and epoxy resin. In addition, the aromatic dihydroxy compound of the present invention is useful for producing a polycarbonate which is stretchable and has a high restoring force.

It is a figure which shows IR spectrum of 1, 3-bis (3-hydroxyphenoxy) benzene. It is a figure which shows IR spectrum of 1, 3-bis (3-methoxyphenoxy) benzene.

Claims (6)

General formula (1):

(Wherein R on the same and different benzene rings each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 4 carbon atoms, m, n, o) Are each independently an integer of 1 to 4, and l is an integer of 1 to 3)
In the presence of a tertiary amine mineral salt in an aprotic polar solvent (excluding N, N-dimethylformamide and N, N-dimethylacetamide). :

(In the formula, R on the same and different benzene rings each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m, n and o each independently represents an integer of 1 to 4; Represents an integer of 1 to 3)
The manufacturing method of the aromatic dihydroxy compound represented by these. The tertiary amine mineral salt is a hydrohalic acid salt of pyridine, and the aprotic polar solvent is represented by the general formula (3):

Wherein R ″ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ′ ″ is an alkyl group having 1 to 4 carbon atoms, X is a carbon atom or nitrogen atom, Y is an oxygen atom or Represents a nitrogen atom, and n represents an integer of 2 to 5. However, when X is a nitrogen atom, R ″ is an alkyl group having 1 to 4 carbon atoms, and when Y is an oxygen atom, the substituent R ′ Does not have '')
The manufacturing method of the aromatic dihydroxy compound of Claim 1 which is a compound represented by these. General formula (4):

(Wherein R on the same and different benzene rings each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and m, n and o each independently represents 1 to An integer of 4 and l represents an integer of 1 to 3)
And a dihalogeno compound represented by the general formula (5):

(In the formula, R ′ represents an alkyl group having 1 to 4 carbon atoms, and M represents an alkali metal)
The aromatic dialkoxy compound represented by the general formula (1) obtained by reacting the alcohol metal salt represented by formula (1) in an aprotic polar solvent is aprotic in the presence of a tertiary amine mineral acid salt. The process for producing an aromatic dihydroxy compound according to claim 1, wherein the reaction is carried out in a polar solvent (except for N, N-dimethylformamide and N, N-dimethylacetamide). The dihalogeno compound is represented by the general formula (6):

(Wherein X represents a halogen atom)
The aromatic dialkoxy compound is represented by the general formula (7):

(In the formula, R ′ represents an alkyl group having 1 to 4 carbon atoms)
The method for producing an aromatic dihydroxy compound according to claim 3, wherein the aromatic dihydroxy compound is 1,3-bis (3-hydroxyphenoxy) benzene. General formula (2):

(In the formula, R on the same and different benzene rings each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m, n and o each independently represents an integer of 1 to 4; Represents an integer of 1 to 3)
An aromatic dihydroxy compound represented by the formula: The aromatic dihydroxy compound according to claim 5, wherein the compound represented by the general formula (2) is 1,3-bis (3-hydroxyphenoxy) benzene.

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